CN103668397B - A kind of high-activity biological gradient cladding for titanium alloy surface - Google Patents
A kind of high-activity biological gradient cladding for titanium alloy surface Download PDFInfo
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Abstract
The present invention discloses a kind of high-activity biological gradient cladding for titanium alloy surface, described coated component is the composite mixed hydroxyapatite (CFHA) of carbonate and fluorion, gradient cladding from inside to outside Oil repellent successively decreases (3.8wt% ~ 0), and carbonate content increases progressively (0 ~ 8wt%).The method of application electrophoretic deposition-sintering, on titanium alloy substrate, the biological gradient coating of dopant ion graded is prepared by fluorine and carbonate substitute amount in adjustment CFHA, the thickness of gradient cladding is controlled by change deposition voltage and depositing time, deposition voltage is 20V ~ 80V, total depositing time is 10s ~ 90s, eventually passes CO
2after sintering processes under protective atmosphere, coating and matrix bonding properties excellent, coating has good biocompatibility, therefore has wide market outlook.
Description
Technical field
The present invention relates to medical titanium alloy bioactive coating on surface preparing technical field, be specifically related to a kind of high-activity biological gradient cladding for titanium alloy surface.
Background technology
Bioactive ceramic coating/titanium alloy composite material, had both had enough intensity and toughness, had again good biocompatibility, was widely used as joint prosthesis replacement material.At present, most widely used bio-ceramic coating and preparation method thereof is respectively hydroxyapatite (Hydroxyapatite is abbreviated as HA) and plasma spraying.
The articular surface that plasma spray is coated in complicated shape is difficult to form uniform coating and embrittlement occurs, and facility investment is large.The electrochemical method that the present invention proposes is prepared bio-ceramic coating and is carried out in a mild condition, and therefore substrate and coating interface do not exist thermal stress issues, the phase transformation avoiding pyrolytic coating to cause and embrittlement, is conducive to strengthening the bonding strength between substrate and coating.Electrochemical process is non-linear process, can prepare uniform ceramic coating in the substrate of complex-shaped and porous surface.Coating obtained by electrophoretic deposition is only more closelypacked base substrate, and coating and substrate combinating strength are very low, can be strengthened the combination of coating and matrix by sintering, also makes the densification of base substrate own simultaneously.Without obvious interface in gradient cladding, thus make thermal stresses obtain mitigation, improve bonding strength and the stability of coating.This is that other coating processes can not be compared in conjunction with thermal treatment.
Hydroxyapatite (hydroxyapatite, HA) composition and structure similar to body bone tissue inorganic components, belong to biological active ceramic material.But HA coating single on titanium or titanium alloy matrix cannot meet the requirement of the biological activity of coating and the bonding strength these two aspects of coating and matrix well simultaneously.The major cause lacking bonding strength between matrix and HA coating is that the difference of the thermal expansivity of bi-material is comparatively large, causes the flip-flop of interface region physicals.Therefore, build HA gradient cladding at titanium implant surface and become a study hotspot.The composition of gradient cladding mainly contains: 1. HA and bio-vitric compound; 2. HA and inactive ceramic compound are (as Al
2o
3, ZrO
2, TiO
2); 3. HA and metal composite.Bioactivity glass is modal intermediate layer, and it can by changing the formula adjustment coefficient of expansion.But when pyroprocessing, easily and matrix and coating generation obvious effect, stability and the biology performance of coating are damaged glass.Similarly, HA can keep its structure not to be destroyed at 1300 DEG C, but at oxide compound Al
2o
3, ZrO
2, TiO
2under the prerequisite existed, according to kind and the addition of oxide compound, the decomposition temperature of HA drops to 750 ~ 1150 DEG C, and the calcium phosphate be decomposed to form likely carries out degrading and causes the stripping at coating and interface before HA dissolves.Therefore, for avoiding additional thing to the detrimentally affect of HA coating, doping vario-property can be carried out to regulate and control its performance to HA itself.
In HA, Common Anions is doped with Fluorin doped and carbonate doping.There are some researches show, fluorine substitutes fluorapatite (FA, the Ca that hydroxyl is formed completely
10(PO
4)
6f
2) thermal expansivity (10 × 10
-6k
-1) than HA (13 × 10
-6k
-1) little, with titanium alloy (9.1 ~ 9.8 × 10
-6k
-1) similar thermal expansion coefficient (E.J.Lee, S.H.Lee, H.W.Kim
etal, Biomaterials26 (2005) 3843; J.M.Gomez-Vega,
E.Saiz,A.P.Tomsia
etal,Biomaterials21(2000)105)。Therefore, the amount regulation and control coefficient of expansion is substituted by controlling fluorine; In addition, fluorion substituted hydroxy can improve phosphatic rock solvability, thus significantly improves the stability of coating in physiological liquid; And F
-replace OH
-after, fluorine is large compared with the electronegativity of Sauerstoffatom, by the attraction to hydrogen atom in hydroxyl, OH-F-OH hydrogen bond energy is strengthened, thus in heat-processed OH
-be not easy to slough from the lattice of FHA, and finally cause the raising of FHA thermostability.Therefore, control Oil repellent graded and adjust its thermal expansivity, reduce the unrelieved stress between coating and matrix, improve the problem that HA coating permanent stability are poor.
Carbonate is a kind of foreign ion group that in natural bone phosphatic rock, content is more, and its mass content in bone mineral composition is in 4 ~ 8wt% scope.Hydroxy apatite (CHA) and human bone mineralogical composition closer to, the existence of carbonate may contribute to meeting human body natural's bone should have certain stability again may by the physiological requirements of normal absorption, therefore, CHA has the biology performance more excellent than HA.But due to carbonate poor heat stability, common CHA coating or film obtain mainly through low temperature depositing or biomineralization, and CHA is combined by weak bond with matrix, and bonding strength is very low, and carbonate content is wayward.Therefore, prepared the CHA of controlled carbonate content by the precipitator method, and at CO
2heat-treat in protective atmosphere, the inherent defect of HA coating can be solved.
Ti
6a1
4v matrix surface electrophoretic deposition-sintering process prepares CFHA bioactive gradient coated material, and there is not been reported both at home and abroad.
Summary of the invention
The technical problem to be solved in the present invention is to provide the gradient cladding for titanium alloy surface of a kind of high-bond and high biological activity.
For solving above technical problem, technical scheme of the present invention is: a kind of high-activity biological gradient cladding for titanium alloy surface, it is characterized in that: with fluorion and the composite mixed phosphatic rock of carbanion for raw material, reduce gradually by fluorine substitutional ion and substitute with carbanion the order increased gradually and successively phosphatic rock galvanic deposit is formed gradient cladding at titanium alloy surface, the content of described gradient cladding fluorion is from inside to outside 3.8 ~ 0wt%, and the content of carbanion is 0 ~ 8wt%.
Described titanium alloy is Ti
6a1
4v alloy.
Described gradient cladding bottom content of fluoride ion 3 ~ 3.8wt%, carbanion content 0 ~ 2wt%, coat-thickness is 10 ~ 30 μm; Gradient cladding transition layer Oil repellent 1 ~ 3wt%, carbonate content 2 ~ 4wt%, coat-thickness is 10 ~ 40 μm; Gradient cladding top layer Oil repellent 0 ~ 1wt%, carbonate content 4 ~ 8wt%, coat-thickness is 5 ~ 20 μm.
The preparation method of the above-mentioned high-activity biological gradient cladding for titanium alloy surface, is characterized in that comprising the following steps:
The first step: prepare fluorion and the composite mixed apatite powder of carbanion
(1) solution preparation: preparation Ca (NO
3)
24H
2o and (NH
4)
2hPO
4solution, the ratio of control n [Ca]/n [P] is 1.67, and at n [CO
3]/n [PO
4] be 0 ~ 0.3, n [F]/n [Ca] be 0 ~ 0.2 scope in determine F ion and CO
3the value of ion, then by a certain amount of NH
4f and NaHCO
3add (NH to
4)
2hPO
4uniform stirring in solution, until solid fully dissolves;
(2) titration: by aforementioned (NH
4)
2hPO
4, NH
4f and NaHCO
3mixing solutions be added drop-wise to Ca (NO lentamente by constant flow pump
3)
24H
2in O solution, vigorous stirring while titration, keep the pH value of mixed solution to be not less than 11 with ammoniacal liquor, temperature of reaction is controlled by water-bath automatic constant-temperature, and after reacting completely, mixed solution continues stirring 2 ~ 12h under being placed in room temperature;
(3) by after the mixed solution ageing after stirring, be washed till neutrality with distilled water wash, suction filtration, ethanol, drying and grinding is crossed 200 ~ 325 mesh sieves and is obtained composite mixed apatite powder;
Second step: titanium alloy surface is by the pre-treatment of polishing, polishing, oil removing and bronsted lowry acids and bases bronsted lowry;
3rd step: electrophoretic deposition gradient cladding
Dehydrated alcohol is poured in stainless steel vessel; be 4 ~ 4.5 by the pH value of dilute hydrochloric acid regulator solution; by the order obtain solution of high fluorine low-carbon (LC) graded to low fluorine high-carbon; the mass concentration of total soluble matters is 5 ~ 30g/L, ultrasonic vibration 1 ~ 2h, take stainless steel vessel as anode; be negative electrode through pretreated titanium sheet; carry out constant voltage electrophoretic deposition, deposition voltage 20 ~ 80V, total depositing time 10 ~ 90s;
4th step: adopt CO
2gas shield heat treatment technics carries out galvanic deposit after heat sintering processes to coating, obtains goods.
In the described the first step, titration process is 2 ~ 10ml/min for controlling titration speed by constant flow pump, and controlling temperature of reaction by water-bath automatic constant-temperature is 0 ~ 90 DEG C; Described ageing process is: mixed solution is left standstill 12 ~ 48h, pours out supernatant liquid, residual mixed liquor is carried out distillation washing, until pH value is 7, finally carries out filtering to obtain filter cake with dehydrated alcohol; Described drying process is: gained filter cake is placed in loft drier in 60 ~ 100 DEG C of drying 12 ~ 48h; Described ground sieved journey is: ground in grinding alms bowl by dry products therefrom, then sieve by 200 ~ 325 mesh sieve.
Sintering heat treatment process in described 4th step is: the painting of electrophoretic deposition be placed in tube-type atmosphere furnace and heat-treat, and protective atmosphere is CO
2gas, flow is 0.5 ~ 1.5L/min.Sintering velocity is 2 ~ 10 DEG C/min, and thermal treatment temp is 600 ~ 1100 DEG C, and soaking time is 1 ~ 4h, and cooling rate is 1 ~ 5 DEG C/min.
The present invention is by carrying out carbanion and fluorion composite doping modification to HA, the regulation and control stability of gradient cladding, the coefficient of expansion and biological activity, avoid the untoward reaction between coated component that the compound such as common phosphatic rock and inactive ceramic, bio-vitric, metal easily causes.Prepared coated material not only can realize graded on composition, improve the matching of matrix and the hot physical performance of coating and mechanical property, thus improve bonding force and the biological activity of coating and matrix, and adopt electrophoretic deposition to control the thickness of gradient cladding, therefore the method has feature that is simple to operate, that regulate and control conveniently, be applicable to the matrix of complicated shape, has very strong industrialization prospect.
Embodiment
Below in conjunction with embodiment, the present invention is further detailed explanation.
embodiment 1
According to the Ca (NO that the mol ratio of n [Ca]/n [P] is 1.67 preparation 1mol/L
3)
24H
2o and 1mol/L (NH
4)
2hPO
4solution, by n [CO
3]/n [PO
4]=0, n [F]/n [Ca]=0.2; N [CO
3]/[PO
4]=0.06, n [F]/n [Ca]=0.1; N [CO
3]/n [PO
4the mol ratio of]=0.2, n [F]/n [Ca]=0 is respectively by appropriate NH
4f and NaHCO
3join (NH
4)
2hPO
4stir in solution, prepare the mixed solution of three kinds of different fluorine and carbonate concentration;
By (NH
4)
2hPO
4, NH
4f and NaHCO
3mixed solution dropwise join Ca (NO lentamente by constant flow pump with the speed of 5ml/min
3)
24H
2in O, vigorous stirring while titration, keeps the pH value of mixed solution to be not less than 11 with ammoniacal liquor, and after reacting completely, mixed solution continues to stir 4h under being placed in room temperature.Mixed solution is left standstill 24h, pours out supernatant liquid, residual mixed liquor is carried out distillation washing, until pH value is 7, finally filter with dehydrated alcohol.Gained filter cake is placed in loft drier in 60 DEG C of dry 48h.Ground in grinding alms bowl by products therefrom, then sieving by 325 mesh sieve finally obtains for above-mentioned three kinds of fluorine of electrophoretic deposition CFHA powder different with carbonate doping;
With 400,600,800, the sand papering titanium alloy substrate of No. 1000, is finally polished to minute surface, is placed in the mixing solutions ultrasonic cleaning 30min oil removing of ethanol and acetone, carries out acid treatment+alkaline purification: dose volume mark is the HNO of 15%
3mixing solutions with the HF of 3%, soaks 1min in the solution by test piece, and distilled water ultrasonic cleaning 15min, soaks 2h by test piece in the NaOH solution of the 1mol/L of 80 DEG C, and successively at distilled water, ultrasonic cleaning 15min in acetone, dries, and preserves;
The dehydrated alcohol measuring 50ml is poured in stainless steel vessel, be 4 by the pH value of dilute hydrochloric acid regulator solution, by the concentration of 10g/L, prepare the deposit fluid of above-mentioned three kinds of CFHA powder respectively, ultrasonic vibration 1.5h, take stainless steel vessel as anode, treated titanium sheet is negative electrode, carries out electrophoretic deposition, and deposition voltage is 40V, the time deposited in every layer of mixed solution is 20s, dries;
The painting of electrophoretic deposition is placed in tube-type atmosphere furnace and carries out CO
2thermal treatment under protective atmosphere, wet CO
2gas flow is 1l/min.Heat-up rate is 2 DEG C/min, and thermal treatment temp is 800 DEG C, and soaking time is 2h, and cooling rate is 1 DEG C/min.Total coating thickness 60 μm, the bonding force of coatings and substrate is 20.6MPa.Titanium sheet after thermal treatment is placed in SBF simulated body fluid to soak 1 week, coatings growth is good.
embodiment 2
According to the Ca (NO that the mol ratio of n [Ca]/n [P] is 1.67 preparation 0.5mol/L
3)
24H
2o and 0.5mol/L (NH
4)
2hPO
4solution, by n [CO
3]/n [PO
4]=0, n [F]/n [Ca]=0.2; N [CO
3]/[PO
4]=0.03, n [F]/n [Ca]=0.14; N [CO
3]/n [PO
4]=0.06, n [F]/n [Ca]=0.1; N [CO
3]/n [PO
4the stoicheiometry of]=0.12, n [F]/n [Ca]=0 is respectively by appropriate NH
4f and NaHCO
3join (NH
4)
2hPO
4stir in solution, prepare the mixed solution of four kinds of different fluorine and carbonate concentration;
By (NH
4)
2hPO
4, NH
4f and NaHCO
3mixed solution dropwise join Ca (NO lentamente by constant flow pump with the speed of 8ml/min
3)
24H
2in O, vigorous stirring while titration, keeps the pH value of mixed solution to be not less than 11 with ammoniacal liquor, and after reacting completely, mixed solution continues to stir 8h under being placed in room temperature.Mixed solution is left standstill 24h, pours out supernatant liquid, residual mixed liquor is carried out distillation washing, until pH value is 7, finally filter with dehydrated alcohol.Gained filter cake is placed in loft drier in 60 DEG C of dry 48h.Ground in grinding alms bowl by products therefrom, then sieving by 325 mesh sieve finally obtains for above-mentioned four kinds of fluorine of electrophoretic deposition CFHA powder different with carbonate doping;
With 400,600,800, the sand papering titanium alloy substrate of No. 1000, finally be polished to minute surface, be placed in the mixing solutions ultrasonic cleaning 30min oil removing of ethanol and acetone, carry out acid treatment+alkaline purification: dose volume mark is 10%HF solution, test piece is soaked 1-2min in the solution, distilled water ultrasonic cleaning 15min, soaks 4h, successively at distilled water by test piece in the NaOH solution of the 1mol/L of 80 DEG C, ultrasonic cleaning 15min in acetone, preserves after drying;
The dehydrated alcohol measuring 50ml is poured in stainless steel vessel, be 4 by the pH value of dilute hydrochloric acid regulator solution, prepare the heavy solution of above-mentioned four kinds of CFHA powder respectively by the concentration of 20g/L, ultrasonic vibration 1h, take stainless steel vessel as anode, treated titanium sheet is negative electrode, carries out electrophoretic deposition, and deposition voltage is 30V, the time deposited successively in every layer of mixed solution is 10s, 15s, 15s, 10s;
The painting of electrophoretic deposition is placed in tube-type atmosphere furnace and carries out CO
2thermal treatment under protective atmosphere, wet CO
2gas flow is 1.5l/min.Heat-up rate is 3 DEG C/min, and thermal treatment temp is 900 DEG C, and soaking time is 2h, and cooling rate is 1 DEG C/min.Every layer thickness is about 10 μm successively, 13 μm, 13 μm, 10 μm, and the bonding force of coatings and substrate is 22.6MPa.Titanium sheet after thermal treatment is placed in SBF simulated body fluid to soak 2 weeks, coatings growth is fine.
embodiment 3
According to the Ca (NO that the mol ratio of n [Ca]/n [P] is 1.67 preparation 0.75mol/L
3)
24H
2o and 0.75mol/L (NH
4)
2hPO
4solution, by n [CO
3]/n [PO
4]=0.02, n [F]/n [Ca]=0.18; N [CO
3]/[PO
4]=0.05, n [F]/n [Ca]=0.14; N [CO
3]/n [PO
4]=0.08, n [F]/n [Ca]=0.08; N [CO
3]/n [PO
4the stoicheiometry of]=0.12, n [F]/n [Ca]=0.02 is respectively by appropriate NH
4f and NaHCO
3join (NH
4)
2hPO
4stir in solution, prepare the mixed solution of four kinds of different fluorine and carbonate concentration;
By (NH
4)
2hPO
4, NH
4f and NaHCO
3mixing solutions dropwise join Ca (NO lentamente by constant flow pump with the speed of 10ml/min
3)
24H
2in O solution, vigorous stirring while titration, the pH value keeping mixed solution with ammoniacal liquor is 11, and after reacting completely, mixed solution continues to stir 6h under being placed in room temperature.Mixed solution is left standstill 24h, pours out supernatant liquid, residual mixed liquor is carried out distillation washing, until pH value is 7, finally filter with dehydrated alcohol.Gained filter cake is placed in loft drier in 60 DEG C of dry 24h.Ground in grinding alms bowl by products therefrom, then sieving by 250 mesh sieve finally obtains for above-mentioned four kinds of fluorine of electrophoretic deposition CFHA powder different with carbonate doping.With 400,600,800, the sand papering titanium alloy substrate of No. 1000, is finally polished to minute surface, is placed in the mixing solutions ultrasonic cleaning 30min oil removing of ethanol and acetone, carries out acid treatment+alkaline purification: dose volume mark is the HNO of 15%
3mixing solutions with the HF of 3%, soaks 1min in the solution by test piece, and distilled water ultrasonic cleaning 15min, soaks 2h by test piece in the NaOH solution of the 1mol/L of 80 DEG C, and successively at distilled water, ultrasonic cleaning 15min in acetone, dries, and preserves;
The dehydrated alcohol measuring 50ml is poured in stainless steel vessel, be 4 by the pH value of dilute hydrochloric acid regulator solution, the deposit fluid of above-mentioned four kinds of CFHA powder is prepared respectively by the concentration of 15g/L, ultrasonic vibration 1.5h, take stainless steel vessel as anode, treated titanium sheet is negative electrode, carry out electrophoretic deposition, deposition voltage is 30V, and the time deposited in every layer of mixed solution is 20s, dries;
The painting of electrophoretic deposition is placed in tube-type atmosphere furnace and carries out CO
2thermal treatment under protective atmosphere, wet CO
2gas flow is 0.5l/min.Heat-up rate is 4 DEG C/min, and thermal treatment temp is 600 DEG C, and soaking time is 2h, and cooling rate is 3 DEG C/min.Coat-thickness is about 65 μm, and the bonding force of coatings and substrate is 15.6MPa.Titanium sheet after thermal treatment is placed in SBF simulated body fluid to soak 2 weeks, coatings growth is good.
embodiment 4
According to the Ca (NO that the mol ratio of n [Ca]/n [P] is 1.67 preparation 1.5mol/L
3)
24H
2o and 1.5mol/L (NH
4)
2hPO
4solution, by n [CO
3]/n [PO
4]=0.02, n [F]/n [Ca]=0.14; N [CO
3]/[PO
4]=0.09, n [F]/n [Ca]=0.09; N [CO
3]/n [PO
4the stoicheiometry of]=0.15, n [F]/n [Ca]=0.04 is respectively by appropriate NH
4f and NaHCO
3join (NH
4)
2hPO
4stir in solution, prepare the mixed solution of three kinds of different fluorine and carbonate concentration;
By (NH
4)
2hPO
4, NH
4f and NaHCO
3mixing solutions dropwise join Ca (NO slowly by constant flow pump with the speed of 4ml/min
3)
24H
2in O, vigorous stirring while titration, the pH value keeping mixed solution with ammoniacal liquor is 11, and after reacting completely, mixed solution continues to stir 8h under being placed in room temperature.Mixed solution is left standstill 24h, pours out supernatant liquid, residual mixed liquor is carried out distillation washing, until pH value is 7, finally filter with dehydrated alcohol.Gained filter cake is placed in loft drier in 100 DEG C of dry 12h.Ground in grinding alms bowl by products therefrom, then sieving by 200 mesh sieve finally obtains for above-mentioned three kinds of fluorine of electrophoretic deposition CFHA powder different with carbonate doping;
With 400,600,800, the sand papering titanium alloy substrate of No. 1000, is finally polished to minute surface, is placed in the mixing solutions ultrasonic cleaning 30min oil removing of ethanol and acetone, carry out acid treatment+alkaline purification: dose volume mark be 15% with 4% the mixing solutions of HF, test piece is soaked 2min in the solution, and distilled water ultrasonic cleaning 15min, soaks 2h by test piece in the NaOH solution of the 1mol/L of 80 DEG C, successively at distilled water, ultrasonic cleaning 15min in acetone, dries, and preserves;
The dehydrated alcohol measuring 50mI is poured in stainless steel vessel, be 4.5 by the pH value of dilute hydrochloric acid regulator solution, preparing the deposit fluid of above-mentioned three kinds of CFHA powder respectively by the concentration of 25g/L, ultrasonic vibration 2h, take stainless steel vessel as anode, treated titanium sheet is negative electrode, carry out electrophoretic deposition, deposition voltage is 50V, and the time deposited successively is 30s, 20s, 20s;
The painting of electrophoretic deposition is placed in tube-type atmosphere furnace and carries out CO
2thermal treatment under protective atmosphere, wet CO
2gas flow is 0.5l/min.Heat-up rate is 5 DEG C/min, and thermal treatment temp is 1100 DEG C, and soaking time is 2h, and cooling rate is 4 DEG C/min.Every layer thickness is about 25 μm successively, 20 μm, 20 μm, and the bonding force of coatings and substrate is 10.2MPa.Titanium sheet after thermal treatment is placed in SBF simulated body fluid to soak 2 weeks, coating and matrix come off.
Claims (5)
1. the high-activity biological gradient cladding for titanium alloy surface, it is characterized in that: with fluorion and the composite mixed phosphatic rock of carbanion for raw material, substitute by fluorion and to reduce gradually and carbanion substitutes the order increased gradually and successively phosphatic rock galvanic deposit formed gradient cladding at titanium alloy surface, the content of described gradient cladding fluorion is from inside to outside 3.8 ~ 0wt%, and the content of carbanion is 0 ~ 8wt%;
Described gradient cladding bottom content of fluoride ion 3 ~ 3.8wt%, carbanion content 0 ~ 2wt%, coat-thickness is 10 ~ 30 μm; Gradient cladding transition layer Oil repellent 1 ~ 3wt%, carbonate content 2 ~ 4wt%, coat-thickness is 10 ~ 40 μm; Gradient cladding top layer Oil repellent 0 ~ 1wt%, carbonate content 4 ~ 8wt%, coat-thickness is 5 ~ 20 μm.
2. the high-activity biological gradient cladding for titanium alloy surface according to claim 1, is characterized in that: described titanium alloy is Ti
6a1
4v alloy.
3., according to the preparation method of the arbitrary described high-activity biological gradient cladding for titanium alloy surface of claim 1-2, it is characterized in that comprising the following steps:
The first step: prepare fluorion and the composite mixed apatite powder of carbanion
(1) solution preparation: preparation Ca (NO
3)
24H
2o and (NH
4)
2hPO
4solution, the ratio of control n [Ca]/n [P] is 1.67, and at n [CO
3]/n [PO
4] be 0 ~ 0.3, n [F]/n [Ca] be 0 ~ 0.2 scope in determine F ion and CO
3the value of ion, then by a certain amount of NH
4f and NaHCO
3add (NH to
4)
2hPO
4uniform stirring in solution, until solid fully dissolves;
(2) titration: by aforementioned (NH
4)
2hPO
4, NH
4f and NaHCO
3mixing solutions be added drop-wise to Ca (NO lentamente by constant flow pump
3)
24H
2in O solution, vigorous stirring while titration, keep the pH value of mixed solution to be not less than 11 with ammoniacal liquor, temperature of reaction is controlled by water-bath automatic constant-temperature, and after reacting completely, mixed solution continues stirring 2 ~ 12h under being placed in room temperature;
(3) by after the mixed solution ageing after stirring, be washed till neutrality with distilled water wash, suction filtration, ethanol, drying and grinding is crossed 200 ~ 325 mesh sieves and is obtained composite mixed apatite powder;
Second step: titanium alloy surface is by the pre-treatment of polishing, polishing, oil removing and bronsted lowry acids and bases bronsted lowry;
3rd step: electrophoretic deposition gradient cladding
Dehydrated alcohol is poured in stainless steel vessel; be 4 ~ 4.5 by the pH value of dilute hydrochloric acid regulator solution; by the order obtain solution of high fluorine low-carbon (LC) graded to low fluorine high-carbon; the mass concentration of total soluble matters is 5 ~ 30g/L, ultrasonic vibration 1 ~ 2h, take stainless steel vessel as anode; be negative electrode through pretreated titanium sheet; carry out constant voltage electrophoretic deposition, deposition voltage 20 ~ 80V, total depositing time 10 ~ 90s;
4th step: adopt CO
2gas shield heat treatment technics carries out galvanic deposit after heat sintering processes to coating, obtains goods.
4. the preparation method of the high-activity biological gradient cladding for titanium alloy surface according to claim 3, it is characterized in that: in the described the first step, titration process is 2 ~ 10mL/min for controlling titration speed by constant flow pump, controlling temperature of reaction by water-bath automatic constant-temperature is 0 ~ 90 DEG C; Described ageing process is: mixed solution is left standstill 12 ~ 48h, pours out supernatant liquid, residual mixed liquor is carried out distillation washing, until pH value is 7, finally carries out filtering to obtain filter cake with dehydrated alcohol; Described drying process is: gained filter cake is placed in loft drier in 60 ~ 100 DEG C of drying 12 ~ 48h; Described ground sieved journey is: ground in grinding alms bowl by dry products therefrom, then sieve by 200 ~ 325 mesh sieve.
5. the preparation method of the high-activity biological gradient cladding for titanium alloy surface according to claim 3; it is characterized in that: the sintering heat treatment process in described 4th step is: the painting of electrophoretic deposition be placed in tube-type atmosphere furnace and heat-treat, and protective atmosphere is CO
2gas, flow is 0.5 ~ 1.5L/min, and sintering velocity is 2 ~ 10 DEG C/min, and thermal treatment temp is 600 ~ 1100 DEG C, and soaking time is 1 ~ 4h, and cooling rate is 1 ~ 5 DEG C/min.
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